Amine sulfonates as dye sites in suspension polymers

ABSTRACT

Ethylenically unsaturated compounds, and especially vinyl chloride and mixtures containing vinyl chloride and acrylonitrile, are copolymerized, in aqueous suspension, with salts of (a) sulfonic acids containing polymerizable ethylenic groups with (b) higher-alkyl-group-containing amino compounds. The resulting copolymers have excellent acceptance for cationic dyes, and are useful in filaments, films and molded articles.

United States Patent Piloni Dec. 2, 1975 AMlNE SULFONATES AS DYE SITES IN 3,538,061 11/1970 Van Gaver 260/785 SUSPENSION POLYMERS 3,547,899 12/1970- Arlt 260/793 3,663,520 5/1972 Balwe 260/875 [75] Inventor: Robert Albert Piloni, Pottstown, Pa.

73 A Th FOREIGN PATENTS OR APPLICATIONS 1 sslgnee f g fi xig'g g g 1,229,737 2 1962 France 260/793 221 Filed: Mar. 20, 1974 OTHER PUBLICATIONS Sorenson, W. R. et al. Preparative Methods of Poly- [21] Appl' 452892 mer Chemistry, Interscience Publishers, N.Y., 1961, p.

Related US. Application Data [63] Continuation of Ser. No. 230,966, March I, 1972,

abandoned, Primary ExaminerChrist0pher A. Henderson, Jr.

[52] US. Cl. 260/79.3 MU; 8/4; 260/63 R; 57 ABSTR CT.

[51] Int Cl 2 COSF l5/40 Ethylenically unsaturated compounds, and especially {58] Fie'ld 60/79 3 MU79 3 R 230 vinyl chloride and mixtures containing vinyl chloride 6 and acrylonitrile, are copolymer'lzed, in aqueous suspension, with salts of (a) sulfonic acids containing [56] References Cited polymerizable ethylenic groups with (b) higher-alkylgroup-containing amino compounds. The resulting co- UNITED STATES PATENTS polymers have excellent acceptance for cationic dyes, 3,075,934 1/1963 Grandine, Jr. 260/29.6 and are useful in filaments, films and molded articles. 3,236,881 2/1966 Distler 260/501 3,260,707 7/1966 Caldwell 260/793 6 Chums, N0 Drawmgs AMINE SULFONATES AS DYE SITES IN SUSPENSION POLYMERS This is a continuation of application Ser. No. 230,966 filed Mar. 1, 1972, now abandoned.

FIELD or THE INVENTION This invention relates to sulfonic-group-containing resins having excellent acceptance of cationic dyes, and to a novel process for the production thereof.

BACKGROUND OF THE INVENTION Various ethylenically unsaturated monomeric compositions have heretofore been copolymerized with simple sulfonic-acid-group-containing monomers to provide polymers which are receptive to cationic dyes. However, it is difficult to conduct such copolymerizations in aqueous systems, such as emulsion or suspension systems, due to the solubility of the sulfonated monomer in the aqueous phase. Accordingly, such copolymerizations are generally carried out in the more expensive and troublesome solvent solution polymerization systems.

It is therefore an object of this invention to provide novel copolymers having good receptivity for cationic dyes. Another object is to provide such copolymers having sulfonic-group-containing monomers therein. A still further object is to provide a process for the production of such resin which can be carried out in aqueous systems such as emulsion or suspension systems.

SUMMARY OF THE INVENTION The above and other objects are secured, in accordance with this invention, in a process which comprises the free-radical-initiated copolymerization, in aqueous suspension of a mixture comprising:

TABLE I Parts by Weight (I) An ethylenically unsaturated I monomer or mixture of such monomers and (II) An amine sulfonate salt of 0.l-l0.0

(II-a) A sulfonic-group-containing ethylenically unsaturated monomer with (II-b) A higher-alkyl-group-containing primary, secondary or tertiary amino compound A particularly preferred subset of the processes of this invention comprises the copolymerization of The polymerization proceeds smoothly, with efficient incorporation of the amine sulfonate salt II into the copolymer. The Products exhibit excellent receptivity for 2 cationic dyes, and may be formed into films, filaments and molded objects.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The Sulfonic-Acid-Group-Containing Monomer (II-a) The sulfonic-acid-group-containing compound providing the anionic novelty of the salt (II) above may be any compound of the formula (ll-9) [Cation [U- 3]- wherein U is an ethylenically unsaturated group of an activity appropriate for copolymerization with the other monomers in the mixture and [Cation 1* indicates a hydrogen ion or appropriate metallic ion. Suitable compounds of this type will be seen to include any allyl or vinyl containing alkyl or aryl sulfonic acid, for. instance styrene sulfonic acid, vinyl sulfonic acid, sulfoethyl methacrylate, 2-acrylamido-2-methylpropane sulfonic acid, methallyl sulfonic acid, a-methyl styrene sulfonic acid, allyl sulfonic acid, ortho methyl styrene sulfonic acid, sulfoethyl acrylate, 2-acrylamido-2- methyl butane sulfonic acid, vinyl benzyl sulfonic acid. In general the criterion of suitability of copolymerizability of the sulfonic-group-containing compound with typical commercial monomers is that it shall be copolymerizable with vinyl chloride, since most such monomers are in the same general area of reactivity. As a rough rule, the criterion of the copolymerizability of the sulfonic compound with vinyl chloride (and by extension, with most other commercial monomers) is that, on a mole percentage basis, an initial charge of 90% vinyl chloride, balance comonom er, shall yield an initial copolymer containing (a)at least vinyl chloride, and (b) not more than 99% vinyl chloride.

The Higher-Alkyl-Group-Containing Amino Compounds -(IIb) The higher fatty amino compound, hereinafter designated (II-b) providing the cationic moiety of the salt (II) may be any compound containing a primary, secondary or tertiary amine group and a higher alkyl group or groups containing a total of from 8 to 30 carbon atoms, such for instance as octyl decyl amine, N-coco beta amino butyric acid (coco signifies the mixed alkyl groups averaging about 12 carbon atoms derived from coconut oil), n-octyl amine, lauryl amine, octadecyl amine, hexadecyl amine, N-coco beta amino propionic acid, di-Z-ethylhexyl amine, di-cyclohexyl amine, n-lauryl-myristyl beta amino propionic acid, dimethyl octyl amine, dimethyl lauryl amine, dimethyl tetradecyl amine, dimethyl hexadecylamine, dimethyl octadecyl amine, dimethyl behenyl amine, tributyl amine, triamyl amine, ethyl methyl octyl amine, dilauryl amine, behenyl amine, diamyl amine, ethyl cyclohexyl amine, long chain ethanol amines and long chain ethoxylated amines.

The Amine Salt II The amine sulfonate salt monomer (Il) may be any salt having its cation derived from the sulfonic compound (II-a) and the amino compound (lI-b). If the monomeric compound (II) is not available as such, it

. may be readily prepared by reacting, in an acidified 3 aqueous medium, a sodium or other salt of the sulfonic acid (II-a) with the amino compound (ll-b). The resultant monomeric salt compound is precipitated and may be recovered by filtration or decantation and then used in the polymerization reaction. Alternatively, since aqueous media are involved, the monomer (II) may be The Ethylenically Unsaturated Monomer (I) As noted above in the Summary of the Invention in Table II, the preferred products are prepared from copolymers of the amine sulfonate salt II with vinyl chloride and mixtures of vinyl chloride with third monomers. As such third monomer, acrylonitrile yields particularly excellent products when employed in the weight proportion of 90-10 parts of acrylonitrile and -90 parts of vinyl chloride. However, still other monomers may be used, either in admixture with vinyl chloride and/or acrylonitrile, or in the absence of these compounds. Examples of such other monomers include, for instance, vinyl acetate, styrene, methacrylates such as methyl methacrylate, di(2-ethyl hexyl) methacrylate, acrylates such as ethyl acrylate, ethyl vinyl ether, methyl vinyl ketone, vinylidene chloride, vinylidene bromide, vinylidene fluoro-chloride and the like; unsaturated hydrocarbons such as ethylene, propylene isobutene, and the like; allyl compounds such as allyl acetate, allyl chloride, allyl ethyl ether and the like; and conjugated and cross-conjugated compounds such as butadiene, isoprene, chloroprene, 2,3-dimethylbutadiene-1,3, piperylene, divinyl ketone, and the like. As noted above in discussing the sulfonic compound(II-9), most practical monomers have activities in the same general range, and are copolymerizable with vinyl chloride; accordingly it may be stated that any monomer which is copolymerizable with vinyl chloride may be used in this invention, with or without vinyl chloride. For a fairly complete list of materials known to copolymerize with vinyl chloride, reference may be had to Krozil: Kurzes Handbuch Der PolymerisationsTechnik-1 l Mehrstoff Polymerization, Edward Bros, Inc., 1945, pp. 735-747, the items under Vinyl chlorid. As a rough rule, the criterion of a practical comonomer for use with vinyl chloride, to produce copolymers containing 80% or more of vinyl chloride is that, on a mole percentage basis, an initial charge of 96% vinyl chloride, balance comonomer, shall yield an initial copolymer containing (a) at least 90% vinyl chloride, and (b) not more than 99% vinyl chloride.

The Polymerization Process The polymerization process of this invention is carried out in suspension in an aqueous medium containing a colloidal-type suspending agent and a free-radical generating agent which is soluble in the monomeric phase. The mass is agitated to keep the monomer in suspension as globules in the medium, and the product is recovered as granules which are physically separated from the aqueous medium at the close of polymeriza: tion. The amine sulfonate salt (II) can either have been previously'prepared and charged to the polymerization reactor mixture as such, or it may be synthesized in situ in the polymerization mass by charging the constituents (the sulfonic acid II-aVOr a salt thereof, and the amino compound II-b) thereof in stoichiometric proportions into the polymerization medium. Alternatively, the amine (II-b), sulfonic acid (II-a) and a small amount of water are added to the other monomers, and agitated therewith. Reaction occurs substantially instantaneously and quantitatively. Preferably the medium should be made slightly acidic, as by the addition of acetic acid, to insure reaction. In those cases where the polymerization rates of the several monomers are disparate, it may be desirable to charge the more rapidly polymerizing monomers incrementally during the polymerization so as to keep its effective concentration constant; for instance, the effective concentration of vinyl chloride or other monomers which are volatile at the polymerization temperature may be kept constant by an isobaric feed procedure wherein the vapor of the volatile monomer is charged continuously at a constant pressure, so that the vapor flows into the reactor as demanded by the ongoing polymerization.

With the foregoing general discussion in mind, there are given herewith detailed examples of the practice of this invention. All parts and percentages are by weight, unless otherwise indicated.

EXAMPLE I COPOLYMERS WITHOUT A THIRD MONOMER Water (deionized) 200 grams 7 Vinyl chloride I00 grams Lauroyl peroxide 1.5 grams Methyl cellulose (I00 centipoise) 2.0 grams Ethylenically unsaturated sulfonic Per Table III compound (Identity per Table III) Higher alkyl group containing Per Table III compound (Identity per Table III) A series of runs was made in accordance with the above schedule, using different sulfonic acid amino compounds in the several runs as tabulated in Table III. In each case the sulfonic compound and amino compound, of the types and amounts selected for the run, were charged together with the water and methyl cellulose, into a polymerization bottle. The water was slightly acidified with acetic acid, and the contents swirled. Reaction was substantially instantaneous, and the amino salt of the sulfonic compound separated out as oily globules. A slight excess of vinyl chloride above the recipe amount was then charged and allowed to evaporate down to the recipe amount (as determined by tare and reweighing) thereby purging the free space in the bottle. The bottle was then sealed with a crown cap having a nitrile rubber seal and a perforation for the hypodermic injection of reactants. The lauroyl peroxide was then injected, and the bottle placed on a polymerizer wheel which dipped and revolved the bottle in a water bath at 50C. for 18 hours. At the end of this time, the unreacted monomers were vented, the bottle was opened, and the granular polymer recovered by filtration and washed on the filter with deionized water. The polymer was then dried on a tray in an oven at C. for 24 hours.

Each resin was dissolved to form a 10% solution in cy clohex'anone and cast as a film on a glass plate, using a ten mil applicator bar. The film was dried on the plate in an oven at 130C. for 15 minutes and then stripped off. The film was then examined forcationic dye acceptance by boiling the same for lS-minutes in a dye bath 6 ate improvement in dye take up, but when even very small proportions of both the styrene sulfonate and N- coco beta amino butyric acid were used, an equal degree of dye take-up was achieved (Run 4). When more of the composition: 5 substantial proportions of both these two components were used, a very marked improvement is achieved Water (buffered to pH 4.0 with 1000 ml. s 5 and sodium acetate) Cationic y gram EXAMPLE Ill (Sevron Red GL", a product of E. l. duPont de Nemours & C0,) MISCELLANEOUS MONOMERS Water (deionized) 200 grams Excellent dye tones were obtained in each case. :gz 'gg ff Slams Set forth herewith are types and amounts of sulfonic Methyl llul se 10o centipoise) 2.0 grams compounds and of higher alkyl containing amino comi P d gorams pounds used in the several runs. Octy ecyl mm a i cf TABLE lll Ethylenically Unsaturated Higher Alkyl Group Run Sulfonic Compound Amino Compound No. Type Grams Used Type Grams Used Sodium styrene N-coco beta amino sulfonate 2.0 propionic acid 2.0 l Sodium methallyl Octyl decyl amine 2.2 2 sulfonate 2.0 Sodium vinyl Same 2.2 3 sulfonate 2.0 Sulfoethyl methacrylate 2.0 Same 2.2 4 2-Acrylamido-2-methyl- Same 2.2 5 propane sulfonic acid 2.0

2-Acrylamido-2-methyl 1 H propane sulfonic acid 0 or 2.0 grams EXAMPLE II (AMPS in Table V) "(perTable'V) TERPOLYMERS WITH ACRYLONITRILE VARYING SULFONATE-AMINE LEVELS A series of polymerization runs was carried out using water (deionized) 200 grams yarious monomer compos tions as set forth hereinafter Vinyl chloride 30 grams in Table V, some containing the amine sulfonate salt, l' 70 and some not. The procedure of Example I wasfol- Sodium styrene sulfonate 0-5 grams (per Table IV) lowed, except of course that the formation of the amine N-COCO beta aminobutyric acid 2 5 1 3 0 sulfonate salt was omitted when its precursors (octyl per a e 4 Methyl cellulose ([00 centipoise) 2.0 grams decyl m l and z'acryl lQ'Q' S pFopane Azoisobutyronitrile 1.5 grams fonic acid in Table V) were omitted. Following are particulars of the several runs.

TABLE V A series of polymerization runs was carried out in accordance with the above schedule, varying the sodium l 2 g 7 8 styrene sulfonate and N-coco beta amino butyric acid from run to run as set forth hereinafter in Table IV. In FW 96 81 85 0 0 0 0 Vinyl acetate 0 0 l5 l5 0 0 0 0 each case the polymerization process and film dyeing Styrene 0 0 0 0 I00 96 O 0 procedure of Example I was followed, except that the so yia x w y g g g 10g 9g o polymerization was carried out at 60 C. instead of 0cm Decyl Amine o 2 2 0 O 2 0 2 C. The dye acceptance of the films was noted sub- Dye Rating 0 6 7 1 0 6 0 s jectively on a scale of 0-10, 0 indicating no dye takeup and 10 indicating that the film was dyed a very deep shade. Following are particulars of the several It will be seen that a variety of monomers other than ns, vinyl chloride (vinyl acetate, styrene, methyl methacry- TABLE Iv late, Runs 3, 6 and 8) may be used in this invention with good results. Also it will be seen that good dyeabil- 5"" ity was obtained with the use of the amine sulfonic salt l 2 3 4 5 6 (Runs 2, 3, 6 and 8) contrasted with poor results in the absence thereof Runs 1 4, 5 and 7 Sodium Styrene Sulfon- 0.0 2.0 0.0 0.1 2.0 5.0 ate Used (grams) N-cocobeta amino 0.0 0.0 2.0 0.1 2.0 5.0 EXAMPLE lv butyric acid used (grams) Vin yl chloride 40 grams Dye Rmmg 2 0 2 7 I0 Acrylonitrile 60 grams Vinyl Sulfonic Acid 2.0 grams Dimethyl Hexadecyl Amine 2.0 grams B t lM ta 0.] ra s It will be seen that the sodium styrene sulfonate alone g zgig s L0 g g in substantial proportions (Run 2) gave only a modergrams Partially hydrolyzed polyvinyl 200.0 grams The vinyl sulfonic acid was added to the acrylonitrile, in which it did not dissolve. Five parts of water and all of the amine were then added and agitated. With mild heating the amine salt formed and dissolved uniformly in the acrylonitrile.

The water, polyvinyl alcohol, azoisobutyronitrile, mercaptan, vinyl chloride and 20 grams of the acrylonitrile-amine salt solution were added to a 2 liter agitated glass autoclave equipped with a heating and cooling jacket.

Polymerization was initiated and maintained at 65 C. The remaining acrylonitrile-amine salt mixture was pumped into the reactor so as to maintain a constant pressure or isobaric polymerization until it was completely used. The polymer was cooled, vented and isolated in the usual way. The polymer was dissolved in 10% dimethyl sulfoxide and spun into fiber. Dyeability was excellent.

From the foregoing general description and detailed specific examples it will be evident that this invention makes possible the production, in the highly economical aqueous polymerization systems, of excellent dyereceptive resins from a wide variety of monomeric materials. The key ingredient involved, the amine salt of the unsaturated sulfonic acid group containing compound is used in minor proportions and is inexpensively and reliably procurable.

I claim:

1. Process of Copolymerizing in an aqueous suspension system .in which the monomers are suspended as globules in an aqueous medium in the presence of a free-radical initiator which is soluble in the mixture (I) specified hereinbelow said aqueous medium containing a colloidal-type suspending agent Parts by Weight (I) A mixture of -10 parts of acrylonitrile with 10-90 parts of vinyl chloride with (ll) an amine sulfonate salt 0.1 [0.0

monomer which is a salt of II-a. an anionic moiety which is 2-acrylamido-2- methyl-propane sulfonic acid with Il-b. a cationic moiety which is a higher-alkylgroup-containing primary, secondary or tertiary amino compound, wherein the alkyl group or groups contain a total of l230 carbon atoms whereby to produce a cationic-dye-receptive polymeric product.

2. Process according to claim 1 wherein the cationic moiety (II-b) is selected from the group consisting of:

N-coco beta-amino propionic acid octyl decyl amine lauryl amine octadecyl amine hexadecyl amine di-2-ethylhexyl amine di-cyclohexyl amine n-lauryl-myristyl beta-amino propionic acid dimethyl lauryl amine dimethyl tetradecyl amine dimethyl hexadecyl amine dimethyl octadecyl amine dimethyl behenyl amine triamyl amine dilauryl amine behenyl amine.

3. Process according to claim 2 wherein the cationic moiety (ll-b) is a primary amine.

4. Process according to claim 2 wherein the cationic moiety (II-b) is a secondary amine.

5. Process according to claim 2 wherein the cationic moiety (II-b) is a tertiary amine.

6. Process according to claim 2 wherein the cationic moiety Il-b) is N-coco beta-amino propionic acid.

C)? 1 J l'ntcnt No. D Decenger Rooaeirfz Albert Piloni Inventcrfis) It is; certified that: error appears in the above-identified patent and that mid Letters Patent are hereby corrected as shown bslow:

Colman 2, line 9, (IL-9) should be (IL-a) Column 5, line 40, (II-9) should. be (IL-a) Column 8, line 45, II-b) should be (II-b) parentheses is missing.

Signcd and Scaled thisthirtieth D f March 1976 [SEAL] Attest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer ('mnmisgimwr ofParenIs and Trademarks 

1. PROCESS OF COPOLYMERIZING IN AN AQUEOUS SUSPENSION SYSTEM IN WHICH THE MONOMERS ARE SUSPENDED AS GLOBULES IN AN AQUEOUS MEDIUM IN THE PRESENCE OF A FREE-RADICAL INITIATOR WHICH IS SOLUBLE IN THE MIXTURE (I) SPECIFIED HEREINBELOW SAID AQUEOUS MEDIUM CONTAINING A COLLOIDAL-TYPE SUSPENDING AGENT
 2. Process according to claim 1 wherein the cationic moiety (II-b) is selected from the group consisting of: N-coco beta-amino propionic acid octyl decyl amine lauryl amine octadecyl amine hexadecyl amine di-2-ethylhexyl amine di-cyclohexyl amine n-lauryl-myristyl beta-amino propionic acid dimethyl lauryl amine dimethyl tetradecyl amine dimethyl hexadecyl amine dimethyl octadecyl amine dimethyl behenyl amine triamyl amine dilauryl amine behenyl amine.
 3. Process according to claim 2 wherein the cationic moiety (II-b) is a primary amine.
 4. Process according to claim 2 wherein the cationic moiety (II-b) is a secondary amine.
 5. Process according to claim 2 wherein the cationic moiety (II-b) is a tertiary amine.
 6. Process according to claim 2 wherein the cationic moiety II-b) is N-coco beta-amino propionic acid. 